Niobium-doped nanofibers elaborated by facile, single-step electrospinning present a higher rate capability in electrochemical cycling experiments than nondoped materials. This is attributed to the reduction of Li+ diffusion path lengths and enhanced intimate interparticle contact, in combination with improved intraparticle conductivity. Niobium doping has a significant effect on the electronic structure and provokes a substantial decrease in particle size.